Retracted: Determination of scutellarin isomer,a predominant metabolite of scutellarin,in human plasma by HPLC/tandem mass spectrometry and its application to a pharmacokinetic study in Chinese healthy volunteers

Retraction: The following article from Biomedical Chromatography, “Determination of scutellarin isomer, a predominant metabolite of scutellarin, in human plasma by HPLC/tandem mass spectrometry and its application to the pharmacokinetic study in Chinese healthy volunteers” by Chun‐hua Xia, Yu‐qing Xiong, and Guang‐ji Wang, published online on 21 June 2007 in Wiley Interscience (www.interscience.wiley.com/journal/bmc), has been retracted at the authors' request.     

Convergence in probability for perturbed stochastic integral equations

Summary In this work, one considers two stochastic integral equations indexed by some parameter and one studies the contiguity of their solutions when the parameter converges to some ₀. Two types of behaviour are described; they lead to the notion of regular and singular perturbations. The method which is used also enables a study of the rate of convergence. Applications to time discretization of equations are given.     

The investigation of critical parameters in the glycolytic response of single living cells by rapid microspectrofluorometric analysis

Summary NAD(P)H fluorescence emission spectra are recorded from single living cells, by a recently developed multichannel microspectrofluorometric technique, in correlation with the intracellular microelectrophoretic addition of substrate (i. e., glucose-6-P). These spectra may be used as a reference basis in establishing the critical parameters to be followed when the same studies are extended to a variety of cells, submitted to various drug effects or physical treatments. The sum-spectra corresponding to channel by channel (wavelength by wavelength) summation of spectra obtained from various cells within a series, before and after addition of substrate, and their difference spectrum may be normalized and evaluated comparatively. The NAD(P)H emission maximum prior to addition of substrate seems to present a mixture of dehydrogenase-bound and free coenzyme. There is a suggestion that immediately after substrate, i. e., at 5 sec, an increase in free NADH is first observed. While the overall changes in fluorescence intensity associated with substrate are quite large (50–150% increase), the counts (i. e., an expression of photons) associated with shifts in the emission maximum (free vs. bound NAD(P)H changes) are at times barely above noise. Rapid microspectrofluorometry provides in principle the most direct approach for the identification of coenzyme bound to various dehydrogenases in single living cells, but further improvements in spectral resolution and signal-to-noise ratio are required, for a better definition of the spectral shifts which may be observed.

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Zusammenfassung Mit Hilfe einer kürzlich entwickelten Mehrkanal-Mikrospektrofluorometer-Methode wurden von einzelnen lebenden Zellen nach intrazellulär mikroelektrophoretischer Substratzugabe (z. B. Glucose-6-P) NAD(P)H Fluoreszenz-Emissionsspektren aufgenommen. Diese Spektren können als Vergleichsbasis bei der Festsetzung der entscheidenden Parameter verwendet werden, wenn die gleichen Untersuchungen auf eine Reihe von Zellen ausgedehnt werden sollen, die verschiedenen Medikamenteffekten oder physikalischer Behandlung ausgesetzt werden. Die Summenspektren, die der kanalmäßigen (wellenlängenmäßigen) Summierung der Spektren von verschiedenen Zellen innerhalb einer Serie, vor und nach Substratzugabe entsprechen, sowie ihre Differenzspektren können normalisiert und vergleichsweise ausgewertet werden. Das NAD(P)H-Emissionsmaximum vor der Substratzugabe scheint ein Gemisch von freiem und dehydrogenasegebundenem Coenzym darzustellen. Unmittelbar nach Substratzugabe (d. h. nach 5 sec) ist ein Anstieg an freiem NADH das erste Mal zu beobachten. Während die mit dem Substrat einhergehenden Gesamtveränderungen der Fluoreszenzintensität recht groß sind (50–150% Anstieg), sind die Impulse (als Effekt der Photonen), die mit einer Verschiebung im Emissionsmaximum verbunden sind (Veränderungen von freiem und gebundenem NAD(P)H) zu manchen Zeiten kaum höher als das Rauschen. Die rasche Mikrospektrofluorometrie stellt im Prinzip die direkteste Methode zur Identifizierung von Coenzymen dar, die an verschiedenen Dehydrogenasen in einzelnen lebenden Zellen gebunden sind. Weitere Verbesserungen der Spektralauflösung und der Empfindlichkeit (signal-to-noise ratio) sind notwendig, um die Spektralverschiebungen, die beobachtet werden, besser auswerten zu können.

     

Calcul théorique des énergies de divers arrangements géométriques de la molécule (η5-C5H5)2TiCl2

The molecular energy of the complex (η⁵-C₅H₅)₂TiCl₂ has been calculated for experimental geometry and for several hypothetical forms by a semi-empirical CNDO/2 approach. The energy difference between experimental (quasi-tetrahedral) geometry and a planar geometry is ca. 20 kcal mol^?1. This difference is sufficiently high to explain the difficulty of the inversion process.     

Fluorescence from the second excited singlet state of [18] annulenes

The emission spectra of the second excited singlet state of [18] annulene and of monofluoro [18] annulene (in a 3-methylpentane glass at 4 K) are reported. The large energy gap between the first and second excited singlet states inhibits fast internal conversion and favours the appearance of S₂ → S₀ emission. In addition, fluorescence from the S₁ state can be observed in monofluoro [13] annulene by exciting into the S₂ or directly into the S₁ absorption.     

Comportement de LiAlH4 en fonction de la dilution dans la racemisation d'un silane optiquement actif en milieu thf

The optically active methylphenyl-α-naphthylsilane racemises quickly in tetrahydrofuran in the presence of LiAlH₄.Kinetic results show a different behaviour of the hydride depending on its concentration. Activation parameters have been obtained and mechanisms proposed.     

CHEMILUMINESCENCE AND ENERGY TRANSFER FROM SINGLET OXYGEN PAIRS

Abstract— Chemiluminescence and photochemiluminescence of systems generating excited (singlet) molecular oxygen has been studied at low temperature in fluid media. A possible interpretation is proposed: that dimers of singlet oxygen are directly or indirectly responsible for the observed emission, the species [¹δg +¹σg⁺] predominating. Energy transfer to a fluorescent molecule is possible only when conditions of spectral overlap, required for transfer by inductive resonance, are fulfilled. Evidence is also presented for the formation of a transient complex between oxygen and a sensitiser or acceptor molecule [S…O₂], which is the precursor of singlet oxygen in these systems. However, other possible mechanisms cannot be excluded.     

19F NMR chemical shifts of n-F-alkyl compounds

The examination of ¹⁹F chemical shifts for ca. 650 F-alkylated compounds of general formula CF₃(CF₂)_nCF₂X led to the following conclusions: the CF₂ groups α to X are very sensitive to the nature of X, and are spread over a range of 85 ppm. The effect of the length of the F-alkyl chain decreases rapidly, so that δCF₂(α) can already be considered as characteristic of X for n = 1 or 2 for most practical purposes. Solvent effects (in 9 different solvents having ε = 1.8 to 52.1) were found to be rather small except for the F-alkyl iodides. A chart which indicates the domain in which the CF₂(α) resonance signal is to be expected is given for 42 different series of F-alkylated compounds; it is expected to provide the synthetic chemist with a useful tool for the identification and characterization of such compounds.